Methods of using esterquats having acyl groups derived from short-chain monocarboxylic acids and short-chain dicarboxylic acids to improve cosmetic compositions

ABSTRACT

Methods of improving the stability of a composition containing a long-chain esterquat and methods of improving the microbicidal properties of a cosmetic composition are described wherein a short-chain esterquat having acyl groups derived from a mixture of at least one monocarboxylic acid having from 6 to 10 carbon atoms, and at least one dicarboxylic acid having from 2 to 12 carbon atoms is combined with a cosmetic composition.

BACKGROUND OF THE INVENTION

Manufacturers of cosmetic products are not only interested incontinually improving the properties of their products and in meetinggrowing consumer demands, they are also—conversely—seeking to keep thenumber of raw materials used as small as possible in order to arrestincreasing raw material costs by eliminating complexity. For thisreason, there is a particular demand for raw materials which not onlyhave improved properties, but also show additional effects such as, forexample, stabilization (for example in the case of active substances) orthe replacement of other formulation ingredients (for examplepreservatives).

In recent years, cationic surfactants of the esterquat type have growninto important cosmetic raw materials because they not only have gooddermatological compatibility, they also condition the skin and the hair,i.e. provide them with pleasant sensory properties, more especially aparticular softness. The esterquats used for this purpose arequaternized esters of alkanolamines with long-chain fatty acids (C₁₂₋₂₀range) which, unfortunately, sometimes show two disadvantages in the endformulations, i.e. separation of the emulsions or gelation are observedin the event of prolonged storage, particularly under temperaturestress, which are both undesirable to the consumer.

Accordingly, the complex problem addressed by the present invention wasto find a way of enabling relatively long-chain esterquats to be moreeasily and stably incorporated in cosmetic preparations while, at thesame time, saving preservative and also improving the stability ofspecial active ingredients, such as UV filters for example.

BRIEF SUMMARY OF THE INVENTION

The present invention relates, in general, to the field of cosmetologyand, more particularly, to the use of special cationic surfactants forthe production of corresponding preparations.

-   -   (a) monocarboxylic acids containing 6 to 10 carbon atoms and    -   (b) dicarboxylic acids containing 2 to 12 carbon atoms.

It has surprisingly been found that esterquats of which the acylcomponent derives from short-chain fatty acids in combination withdicarboxylic acids facilitate the incorporation of relatively long-chainesterquats. In particular, storage and thermal stability are improvedand the unwanted effect of gelation is counteracted. At the same time,the esterquats to be used in accordance with the invention havemicrobicidal properties so that far less preservative has to be used tostop the cosmetic preparations from spoiling. In some cases, there is noneed whatever to add preservatives. Finally, it was found thatphotolabile active substances, such as UV filters or retinol forexample, are more slowly degraded in the presence of the specialesterquats.

DETAILED DESCRIPTION OF THE INVENTION

“Esterquats” are generally understood to be quaternized fatty acidtriethanolamine ester salts. These are known compounds which can beobtained by the relevant methods of preparative organic chemistry.Reference is made in this connection to International patent applicationWO 91/01295 (Henkel), according to which triethanolamine is partlyesterified with fatty acids in the presence of hypophosphorous acid, airis passed through the reaction mixture and the whole is then quaternizedwith dimethyl sulfate or ethylene oxide. In addition, German patent DE4308794 C1 (Henkel) describes a process for the production of solidesterquats in which the quaternization of triethanolamine esters iscarried out in the presence of suitable dispersants, preferably fattyalcohols. Overviews on this theme have been published by R. Puchta etal. in Tens. Surf. Det., 30, 186 (1993), by M. Brock in Tens. Surf.Det., 30, 394 (1993), by R. Lagerman et al. in J. Am. Oil Chem. Soc.,71, 97 (1994) and by I. Shapiro in Cosm. Toil. 109, 77 (1994).

Typical examples of esterquats suitable for use in accordance with theinvention are products of which the acyl component (a) derives frommonocarboxylic acids corresponding to formula (I):R¹CO—OH  (I)in which R¹CO is an acyl group containing 6 to 10 carbon atoms. Examplesof such monocarboxylic acids are caproic acid, caprylic acid, capricacid and technical mixtures thereof such as, for example, so-calledhead-fractionated fatty acid. Esterquats of which the acyl component (a)derives from monocarboxylic acids of formula (I), in which R¹CO is alinear, saturated acyl group containing 8 to 10 carbon atoms, arepreferably used.

Other esterquats used in accordance with the invention are those ofwhich the acyl component (b) derives from dicarboxylic acidscorresponding to formula (II):HOOC(CH₂)_(n)COOH  (II)in which n is a number of 1 to 10. Examples of such dicarboxylic acidsare malonic acid, succinic acid, maleic acid, fumaric acid, glutaricacid, sorbic acid, pimelic acid, azelaic acid, sebacic acid and/ordodecanedioic acid, but preferably adipic acid. Overall, esterquats ofwhich the acyl component (a) derives from monocarboxylic acidscorresponding to formula (I), where R¹CO is a linear saturated acylgroup containing 6 to 22 carbon atoms, and of which the acyl component(b) derives from adipic acid are preferably used. The molar ratio ofcomponent (a) to component (b) may be in the range from 1:99 to 99:1 andis preferably in the range from 50:50 to 90:10 and more particularly inthe range from 70:30 to 80:20.

A special embodiment of the invention is characterized by the use ofesterquats which represent quaternized fatty acid triethanolamine estersalts corresponding to formula (III):

in which R¹CO stands for mixtures of mono- and dicarboxylic acids, R²and R³ independently of one another represent hydrogen or have the samemeaning as R¹CO, R⁴ is an alkyl group containing 1 to 4 carbon atoms ora (CH₂CH₂O)_(q)H group, m, n and p together stand for 0 or numbers of 1to 12, q is a number of 1 to 12 and X is halide, alkyl sulfate or alkylphosphate.

Besides the quaternized fatty acid triethanolamine ester salts, othersuitable esterquats are quaternized ester salts of mono-/dicarboxylicacid mixtures with diethanolalkyamines corresponding to formula (IV):

in which R¹CO represents mixtures of mono- and dicarboxylic acids, R² ishydrogen or has the same meaning as R¹CO, R⁴ and R⁵ independently of oneanother are alkyl groups containing 1 to 4 carbon atoms, m and ntogether stand for 0 or numbers of 1 to 12 and X stands for halide,alkyl sulfate or alkyl phosphate.

Another group of suitable esterquats are the quaternized ester salts ofmono-/dicarboxylic acid mixtures with 1,2-dihydroxypropyl dialkylaminescorresponding to formula (V):

in which R¹CO represents mixtures of mono- and dicarboxylic acids, R² ishydrogen or has the same meaning as R¹CO, R⁴, R⁶ and R⁷ independently ofone another are alkyl groups containing 1 to 4 carbon atoms, m and ntogether stand for 0 or numbers of 1 to 12 and X stands for halide,alkyl sulfate or alkyl phosphate.

In addition, other suitable esterquats are substances in which the esterbond is replaced by an amide bond and which—preferably based ondiethylenetriamine—correspond to formula (VI):

in which R¹CO represents mixtures of mono- and dicarboxylic acids, R² ishydrogen or has the same meaning as R¹CO, R⁶ and R⁷ independently of oneanother are alkyl groups containing 1 to 4 carbon atoms and X is halide,alkyl sulfate or alkyl phosphate. Amide esterquats such as these arecommercially obtainable, for example, under the name of Incroquat®(Croda).

Finally, other suitable esterquats are compounds based on ethoxylatedcastor oil or hydrogenation products thereof which preferably correspondto formula (VII):

in which R⁸CO represents mixtures of mono- and dicarboxylic acids, A isa linear or branched alkylene group containing 1 to 6 carbon atoms, R⁹,R¹⁰ and R¹¹ independently of one another represent hydrogen or a C₁₋₄alkyl group, R¹² is a C₁₋₄ alkyl group or a benzyl group and X ishalogen, alkyl sulfate or alkyl phosphate.

So far as the choice of the preferred fatty acids and the optimal degreeof esterification are concerned, the examples mentioned for (III) alsoapply to the esterquats corresponding to formulae (IV) to (VII).

The esterquats corresponding to formulae (III) to (VII) may be obtainedboth from fatty acids and from the corresponding triglycerides inadmixture with the corresponding dicarboxylic acids. One such process,which is intended to be representative of the relevant prior art, isproposed in European patent EP 0750606 B1 (Cognis).

To produce the quaternized esters, the mixtures of mono- anddicarboxylic acids and the triethanolamine—based on the availablecarboxyl functions—may be used in a molar ratio of 1.1:1 to 3:1. Withthe performance properties of the esterquats in mind, a ratio of 1.2:1to 2.2:1 and preferably 1.5:1 to 1.9:1 has proved to be particularlyadvantageous.

The preferred esterquats are technical mixtures of mono-, di- andtriesters with an average degree of esterification of 1.5 to 1.9.

Commercial Applications

The special esterquats are used for the production of cosmeticpreparations in which they may be present in quantities of 0.1 to 10,preferably 1 to 8 and more particularly 2 to 5% by weight, based on thepreparations. These preparations are preferably skin or hair treatmentpreparations which may also contain other auxiliaries and additivestypical of such preparations. These include, for example, mildsurfactants, oil components, emulsifiers, pearlizing waxes, consistencyfactors, thickeners, superfatting agents, stabilizers, polymers,silicone compounds, fats, waxes, lecithins, phospholipids, biogenicagents, UV protection factors, antioxidants, deodorizers,antiperspirants, antidandruff agents, film formers, swelling agents,insect repellents, self-tanning agents, tyrosine inhibitors(depigmenting agents), hydrotropes, solubilizers, preservatives, perfumeoils, dyes and the like.

Surfactants

Suitable surfactants are anionic, nonionic, cationic and/or amphotericor zwitterionic surfactants which are normally present in thepreparations in quantities of about 1 to 70, preferably 5 to 50 and moreparticularly 10 to 30% by weight. Typical examples of anionicsurfactants are soaps, alkyl benzenesulfonates, alkanesulfonates, olefinsulfonates, alkylether sulfonates, glycerol ether sulfonates, α-methylester sulfonates, sulfofatty acids, alkyl sulfates, fatty alcohol ethersulfates, glycerol ether sulfates, fatty acid ether sulfates, hydroxymixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide(ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylicacids and salts thereof, fatty acid isethionates, fatty acidsarcosinates, fatty acid taurides, N-acylamino acids such as, forexample, acyl lactylates, acyl tartrates, acyl glutamates and acylaspartates, alkyl oligoglucoside sulfates, protein fatty acidcondensates (particularly wheat-based vegetable products) and alkyl(ether)phosphates. If the anionic surfactants contain polyglycol etherchains, they may have a conventional homolog distribution although theypreferably have a narrow-range homolog distribution. Typical examples ofnonionic surfactants are fatty alcohol polyglycol ethers, alkylphenolpolyglycol ethers, fatty acid polyglycol esters, fatty acid amidepolyglycol ethers, fatty amine polyglycol ethers, alkoxylatedtriglycerides, mixed ethers and mixed formals, optionally partlyoxidized alk(en)yl oligoglycosides or glucuronic acid derivatives, fattyacid-N-alkyl glucamides, protein hydrolyzates (particularly wheat-basedvegetable products), polyol fatty acid esters, sugar esters, sorbitanesters, polysorbates and amine oxides. If the nonionic surfactantscontain polyglycol ether chains, they may have a conventional homologdistribution, although they preferably have a narrow-range homologdistribution. Typical examples of cationic surfactants are quaternaryammonium compounds such as, for example, dimethyl distearyl ammoniumchloride and other esterquats, more particularly quaternized fatty acidtrialkanolamine ester salts. Typical examples of amphoteric orzwitterionic surfactants are alkylbetaines, alkylamidobetaines,aminopropionates, aminoglycinates, imidazolinium betaines andsulfobetaines. The surfactants mentioned are all known compounds.Information on their structure and production can be found in relevantsynoptic works, cf. for example J. Falbe (ed.), “Surfactants in ConsumerProducts”, Springer Verlag, Berlin, 1987, pages 54 to 124 or J. Falbe(ed.), “Katalysatoren, Tenside und Mineralöladditive (Catalysts,Surfactants and Mineral Oil Additives)”, Thieme Verlag, Stuttgart, 1978,pages 123-217. Typical examples of particularly suitable mild, i.e.particularly dermatologically compatible, surfactants are fatty alcoholpolyglycol ether sulfates, monoglyceride sulfates, mono- and/or dialkylsulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fattyacid taurides, fatty acid glutamates, α-olefin sulfonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acid glucamides,alkylamidobetaines, amphoacetals and/or protein fatty acid condensates,preferably based on wheat proteins.

Oil Components

Suitable oil components are, for example, Guerbet alcohols based onfatty alcohols containing 6 to 18 and preferably 8 to 10 carbon atoms,esters of linear C₆₋₂₂ fatty acids with linear or branched C₆₋₂₂ fattyalcohols or esters of branched C₆₋₁₃ carboxylic acids with linear orbranched C₆₋₂₂ fatty alcohols such as, for example, myristyl myristate,myristyl palmitate, myristyl stearate, myristyl isostearate, myristyloleate, myristyl behenate, myristyl erucate, cetyl myristate, cetylpalmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetylbehenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearylstearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearylerucate, isostearyl myristate, isostearyl palmitate, isostearylstearate, isostearyl isostearate, isostearyl oleate, isostearylbehenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleylstearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleylerucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenylisostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucylmyristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyloleate, erucyl behenate and erucyl erucate. Also suitable are esters oflinear C₆₋₂₂ fatty acids with branched alcohols, more particularly2-ethyl hexanol, esters of C₁₈₋₃₈ alkylhydroxycarboxylic acids withlinear or branched C₆₋₂₂ fatty alcohols (cf. DE 197 56 377 A1), moreespecially Dioctyl Malate, esters of linear and/or branched fatty acidswith polyhydric alcohols (for example propylene glycol, dimer diol ortrimer triol) and/or Guerbet alcohols, triglycerides based on C₆₋₁₀fatty acids, liquid mono-, di- and triglyceride mixtures based on C₆₋₁₈fatty acids, esters of C₆₋₂₂ fatty alcohols and/or Guerbet alcohols witharomatic carboxylic acids, more particularly benzoic acid, esters ofC₂₋₁₂ dicarboxylic acids with linear or branched alcohols containing 1to 22 carbon atoms or polyols containing 2 to 10 carbon atoms and 2 to 6hydroxyl groups, vegetable oils, branched primary alcohols, substitutedcyclohexanes, linear and branched C₆₋₂₂ fatty alcohol carbonates suchas, for example, Dicaprylyl Carbonate (Cetiol® CC), Guerbet carbonatesbased on fatty alcohols containing 6 to 18 and preferably 8 to 10 carbonatoms, esters of benzoic acid with linear and/or branched C₆₋₂₂ alcohols(for example Finsolv® TN), linear or branched, symmetrical ornonsymmetrical dialkyl ethers containing 6 to 22 carbon atoms per alkylgroup such as, for example, Dicaprylyl Ether (Cetiol® OE), ring openingproducts of epoxidized fatty acid esters with polyols, silicone oils(Cyclomethicone, silicon methicone types, etc.) and/or aliphatic ornaphthenic hydrocarbons, for example squalane, squalene or dialkylcyclohexanes.

Emulsifiers

Suitable emulsifiers are, for example, nonionic surfactants from atleast one of the following groups:

-   -   products of the addition of 2 to 30 mol ethylene oxide and/or 0        to 5 mol propylene oxide onto linear C₈₋₂₂ fatty alcohols,        C₁₂₋₂₂ fatty acids, alkyl phenols containing 8 to 15 carbon        atoms in the alkyl group and alkylamines containing 8 to 22        carbon atoms in the alkyl group;    -   alkyl and/or alkenyl oligoglycosides containing 8 to 22 carbon        atoms in the alk(en)yl group and ethoxylated analogs thereof;    -   adducts of 1 to 15 mol ethylene oxide with castor oil and/or        hydrogenated castor oil;    -   adducts of 15 to 60 mol ethylene oxide with castor oil and/or        hydrogenated castor oil;    -   partial esters of glycerol and/or sorbitan with unsaturated,        linear or saturated, branched fatty acids containing 12 to 22        carbon atoms and/or hydroxycarboxylic acids containing 3 to 18        carbon atoms and adducts thereof with 1 to 30 mol ethylene        oxide;    -   partial esters of polyglycerol (average degree of        self-condensation 2 to 8), polyethylene glycol (molecular weight        400 to 5000), trimethylolpropane, pentaerythritol, sugar        alcohols (for example sorbitol), alkyl glucosides (for example        methyl glucoside, butyl glucoside, lauryl glucoside) and        polyglucosides (for example cellulose) with saturated and/or        unsaturated, linear or branched fatty acids containing 12 to 22        carbon atoms and/or hydroxycarboxylic acids containing 3 to 18        carbon atoms and adducts thereof with 1 to 30 mol ethylene        oxide;    -   mixed esters of pentaerythritol, fatty acids, citric acid and        fatty alcohol according to DE 1165574 PS and/or mixed esters of        fatty acids containing 6 to 22 carbon atoms, methyl glucose and        polyols, preferably glycerol or polyglycerol,    -   mono-, di- and trialkyl phosphates and mono-, di- and/or        tri-PEG-alkyl phosphates and salts thereof,    -   wool wax alcohols,    -   polysiloxane/polyalkyl/polyether copolymers and corresponding        derivatives,    -   block copolymers, for example Polyethylene glycol-30        Dipolyhydroxystearate;    -   polymer emulsifiers, for example Pemulen types (TR-1, TR-2) of        Goodrich;    -   polyalkylene glycols and    -   glycerol carbonate.        Ethylene Oxide Addition Products

The addition products of ethylene oxide and/or propylene oxide withfatty alcohols, fatty acids, alkylphenols or with castor oil are knowncommercially available products. They are homolog mixtures of which theaverage degree of alkoxylation corresponds to the ratio between thequantities of ethylene oxide and/or propylene oxide and substrate withwhich the addition reaction is carried out. C_(12/18) fatty acidmonoesters and diesters of adducts of ethylene oxide with glycerol areknown as lipid layer enhancers for cosmetic formulations from DE 20 24051 PS.

Alkyl and/or Alkenyl Oligoglycosides

Alkyl and/or alkenyl oligoglycosides, their production and their use areknown from the prior art. They are produced in particular by reactingglucose or oligosaccharides with primary alcohols containing 8 to 18carbon atoms. So far as the glycoside unit is concerned, bothmonoglycosides in which a cyclic sugar unit is attached to the fattyalcohol by a glycoside bond and oligomeric glycosides with a degree ofoligomerization of preferably up to about 8 are suitable. The degree ofoligomerization is a statistical mean value on which the homologdistribution typical of such technical products is based.

Partial Glycerides

Typical examples of suitable partial glycerides are hydroxystearic acidmonoglyceride, hydroxystearic acid diglyceride, isostearic acidmonoglyceride, isostearic acid diglyceride, oleic acid monoglyceride,oleic acid diglyceride, ricinoleic acid monoglyceride, ricinoleic aciddiglyceride, linoleic acid monoglyceride, linoleic acid diglyceride,linolenic acid monoglyceride, linolenic acid diglyceride, erucic acidmonoglyceride, erucic acid diglyceride, tartaric acid monoglyceride,tartaric acid diglyceride, citric acid monoglyceride, citric aciddiglyceride, malic acid monoglyceride, malic acid diglyceride andtechnical mixtures thereof which may still contain small quantities oftriglyceride from the production process. Addition products of 1 to 30and preferably 5 to 10 mol ethylene oxide onto the partial glyceridesmentioned are also suitable.

Sorbitan Esters

Suitable sorbitan esters are sorbitan monoisostearate, sorbitansesquiisostearate, sorbitan diisostearate, sorbitan triisostearate,sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitantrioleate, sorbitan monoerucate, sorbitan sesquierucate, sorbitandierucate, sorbitan trierucate, sorbitan monoricinoleate, sorbitansesquiricinoleate, sorbitan diricinoleate, sorbitan triricinoleate,sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitandihydroxystearate, sorbitan trihydroxystearate, sorbitan monotartrate,sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate,sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate,sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate,sorbitan dimaleate, sorbitan trimaleate and technical mixtures thereof.Addition products of 1 to 30 and preferably 5 to 10 mol ethylene oxideonto the sorbitan esters mentioned are also suitable.

Polyglycerol Esters

Typical examples of suitable polyglycerol esters are Polyglyceryl-2Dipolyhydroxystearate (Dehymuls® PGPH), Polyglycerin-3-Diisostearate(Lameform® TGI), Polyglyceryl-4 Isostearate (Isolan® GI 34),Polyglyceryl-3 Oleate, Diisostearoyl Polyglyceryl-3 Diisostearate(Isolan® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care® 450),Polyglyceryl-3 Beeswax (Cera Bellina®), Polyglyceryl-4 Caprate(Polyglycerol Caprate T2010/90), Polyglyceryl-3 Cetyl Ether (Chimexane®NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and PolyglycerylPolyricinoleate (Admul® WOL 1403), Polyglyceryl Dimerate Isostearate andmixtures thereof. Examples of other suitable polyolesters are the mono-,di- and triesters of trimethylol propane or pentaerythritol with lauricacid, cocofatty acid, tallow fatty acid, palmitic acid, stearic acid,oleic acid, behenic acid and the like optionally reacted with 1 to 30mol ethylene oxide.

Anionic Emulsifiers

Typical anionic emulsifiers are aliphatic C₁₂₋₂₂ fatty acids, such aspalmitic acid, stearic acid or behenic acid for example, and C₁₂₋₂₂dicarboxylic acids, such as azelaic acid or sebacic acid for example.

Amphoteric and Cationic Emulsifiers

Other suitable emulsifiers are zwitterionic surfactants. Zwitterionicsurfactants are surface-active compounds which contain at least onequaternary ammonium group and at least one carboxylate and one sulfonategroup in the molecule. Particularly suitable zwitterionic surfactantsare the so-called betaines, such as the N-alkyl-N,N-dimethyl ammoniumglycinates, for example cocoalkyl dimethyl ammonium glycinate,N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for examplecocoacylaminopropyl dimethyl ammonium glycinate, and2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18carbon atoms in the alkyl or acyl group and cocoacylaminoethylhydroxyethyl carboxymethyl glycinate. The fatty acid amide derivativeknown under the CTFA name of Cocamidopropyl Betaine is particularlypreferred. Ampholytic surfactants are also suitable emulsifiers.Ampholytic surfactants are surface-active compounds which, in additionto a C_(8/18) alkyl or acyl group, contain at least one free amino groupand at least one —COOH or —SO₃H group in the molecule and which arecapable of forming inner salts. Examples of suitable ampholyticsurfactants are N-alkyl glycines, N-alkyl propionic acids,N-alkylaminobutyric acids, N-alkyliminodipropionic acids,N-hydroxyethyl-N-alkylamidopropyl glycines, N-alkyl taurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acidscontaining around 8 to 18 carbon atoms in the alkyl group. Particularlypreferred ampholytic surfactants are N-coco-alkylaminopropionate,cocoacylaminoethyl aminopropionate and C_(12/18) acyl sarcosine.Finally, other suitable emulsifiers are cationic surfactants, those ofthe esterquat type, preferably methyl-quaternized difatty acidtriethanolamine ester salts, being particularly preferred.

Fats and Waxes

Typical examples of fats are glycerides, i.e. solid or liquid, vegetableor animal products which consist essentially of mixed glycerol esters ofhigher fatty acids. Suitable waxes are inter alia natural waxes such as,for example, candelilla wax, carnauba wax, Japan wax, espartograss wax,cork wax, guaruma wax, rice oil wax, sugar cane wax, ouricury wax,montan wax, beeswax, shellac wax, spermaceti, lanolin (wool wax),uropygial fat, ceresine, ozocerite (earth wax), petrolatum, paraffinwaxes and microwaxes; chemically modified waxes (hard waxes) such as,for example, montan ester waxes, sasol waxes, hydrogenated jojoba waxesand synthetic waxes such as, for example, polyalkylene waxes andpolyethylene glycol waxes. Besides the fats, other suitable additivesare fat-like substances, such as lecithins and phospholipids. Lecithinsare known among experts as glycerophospholipids which are formed fromfatty acids, glycerol, phosphoric acid and choline by esterification.Accordingly, lecithins are also frequently referred to by experts asphosphatidyl cholines (PCs). Examples of natural lecithins are thekephalins which are also known as phosphatidic acids and which arederivatives of 1,2-diacyl-sn-glycerol-3-phosphoric acids. By contrast,phospholipids are generally understood to be mono- and preferablydiesters of phosphoric acid with glycerol (glycerophosphates) which arenormally classed as fats. Sphingosines and sphingolipids are alsosuitable.

Pearlizing Waxes

Suitable pearlizing waxes are, for example, alkylene glycol esters,especially ethylene glycol distearate; fatty acid alkanolamides,especially cocofatty acid diethanolamide; partial glycerides, especiallystearic acid monoglyceride; esters of polybasic, optionallyhydroxysubstituted carboxylic acids with fatty alcohols containing 6 to22 carbon atoms, especially long-chain esters of tartaric acid; fattycompounds, such as for example fatty alcohols, fatty ketones, fattyaldehydes, fatty ethers and fatty carbonates which contain in all atleast 24 carbon atoms, especially laurone and distearylether; fattyacids, such as stearic acid, hydroxystearic acid or behenic acid, ringopening products of olefin epoxides containing 12 to 22 carbon atomswith fatty alcohols containing 12 to 22 carbon atoms and/or polyolscontaining 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixturesthereof.

Consistency Factors and Thickeners

The consistency factors mainly used are fatty alcohols or hydroxyfattyalcohols containing 12 to 22 and preferably 16 to 18 carbon atoms andalso partial glycerides, fatty acids or hydroxyfatty acids. Acombination of these substances with alkyl oligoglucosides and/or fattyacid N-methyl glucamides of the same chain length and/or polyglycerolpoly-12-hydroxystearates is preferably used. Suitable thickeners are,for example, Aerosil® types (hydrophilic silicas), polysaccharides, moreespecially xanthan gum, guar-guar, agar-agar, alginates and tyloses,carboxymethyl cellulose and hydroxyethyl and hydroxypropyl cellulose,also relatively high molecular weight polyethylene glycol monoesters anddiesters of fatty acids, polyacrylates (for example Carbopols® andPemulen types [Goodrich]; Synthalens® [Sigma]; Keltrol types [Kelco];Sepigel types [Seppic]; Salcare types [Allied Colloids]),polyacrylamides, polymers, polyvinyl alcohol and polyvinyl pyrrolidone.Other consistency factors which have proved to be particularly effectiveare bentonites, for example Bentone® Gel VS-5PC (Rheox) which is amixture of cyclopentasiloxane, Disteardimonium Hectorite and propylenecarbonate. Other suitable consistency factors are surfactants such as,for example, ethoxylated fatty acid glycerides, esters of fatty acidswith polyols, for example pentaerythritol or trimethylol propane,narrow-range fatty alcohol ethoxylates or alkyl oligoglucosides andelectrolytes, such as sodium chloride and ammonium chloride.

Superfatting Agents

Superfatting agents may be selected from such substances as, forexample, lanolin and lecithin and also polyethoxylated or acylatedlanolin and lecithin derivatives, polyol fatty acid esters,monoglycerides and fatty acid alkanolamides, the fatty acidalkanolamides also serving as foam stabilizers.

Stabilizers

Metal salts of fatty acids such as, for example, magnesium, aluminiumand/or zinc stearate or ricinoleate may be used as stabilizers.

Polymers

Suitable cationic polymers are, for example, cationic cellulosederivatives such as, for example, the quaternized hydroxyethyl celluloseobtainable from Amerchol under the name of Polymer JR 400®, cationicstarch, copolymers of diallyl ammonium salts and acrylamides,quaternized vinyl pyrrolidone/vinyl imidazole polymers such as, forexample, Luviquat® (BASF), condensation products of polyglycols andamines, quaternized collagen polypeptides such as, for example,Lauryidimonium Hydroxypropyl Hydrolyzed Collagen (Lamequat® L, Grünau),quaternized wheat polypeptides, polyethyleneimine, cationic siliconepolymers such as, for example, amodimethicone, copolymers of adipic acidand dimethylamino-hydroxypropyl diethylenetriamine (Cartaretine®,Sandoz), copolymers of acrylic acid with dimethyl diallyl ammoniumchloride (Merquat® 550, Chemviron), polyaminopolyamides as described,for example, in FR 2252840 A and crosslinked water-soluble polymersthereof, cationic chitin derivatives such as, for example, quaternizedchitosan, optionally in microcrystalline distribution, condensationproducts of dihaloalkyls, for example dibromobutane, withbis-dialkylamines, for example bis-dimethylamino-1,3-propane, cationicguar gum such as, for example, Jaguar®CBS, Jaguar®C-17, Jaguar®C-16 ofCelanese, quaternized ammonium salt polymers such as, for example,Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 of Miranol.

Suitable anionic, zwitterionic, amphoteric and nonionic polymers are,for example, vinyl acetate/crotonic acid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butylmaleate/isobornyl acrylate copolymers, methyl vinylether/maleicanhydride copolymers and esters thereof, uncrosslinked andpolyol-crosslinked polyacrylic acids, acrylamidopropyl trimethylammoniumchloride/acrylate copolymers, octylacrylamide/methylmethacrylate/tert.-butylaminoethyl methacrylate/2-hydroxypropylmethacrylate copolymers, polyvinyl pyrrolidone, vinyl pyrrolidone/vinylacetate copolymers, vinyl pyrrolidone/dimethylaminoethylmethacrylate/vinyl caprolactam terpolymers and optionally derivatizedcellulose ethers and silicones. Other suitable polymers and thickenerscan be found in Cosm. Toil., 108, 95 (1993).

Silicone Compounds

Suitable silicone compounds are, for example, dimethyl polysiloxanes,methylphenyl polysiloxanes, cyclic silicones and amino-, fatty acid-,alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/oralkyl-modified silicone compounds which may be both liquid andresin-like at room temperature. Other suitable silicone compounds aresimethicones which are mixtures of dimethicones with an average chainlength of 200 to 300 dimethylsiloxane units and hydrogenated silicates.A detailed overview of suitable volatile silicones can be found in Toddet al. in Cosm. Toil. 91, 27 (1976).

UV Protection Factors and Antioxidants

UV protection factors in the context of the invention are, for example,organic substances (light filters) which are liquid or crystalline atroom temperature and which are capable of absorbing ultravioletradiation and of releasing the energy absorbed in the form oflonger-wave radiation, for example heat. UV-B filters can be oil-solubleor water-soluble. The following are examples of oil-soluble substances:

-   -   3-benzylidene camphor or 3-benzylidene norcamphor and        derivatives thereof, for example 3-(4-methylbenzylidene)-camphor        as described in EP 0693471 B1;    -   4-aminobenzoic acid derivatives, preferably        4-(dimethylamino)-benzoic acid-2-ethylhexyl ester,        4-(dimethylamino)-benzoic acid-2-octyl ester and        4-(dimethylamino)-benzoic acid amyl ester;    -   esters of cinnamic acid, preferably 4-methoxycinnamic        acid-2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester,        4-methoxycinnamic acid isoamyl ester, 2-cyano-3,3-phenylcinnamic        acid-2-ethylhexyl ester (Octocrylene);    -   esters of salicylic acid, preferably salicylic acid-2-ethylhexyl        ester, salicylic acid-4-isopropylbenzyl ester, salicylic acid        homomenthyl ester;    -   derivatives of benzophenone, preferably        2-hydroxy-4-methoxybenzophenone,        2-hydroxy4-methoxy-4′-methylbenzophenone,        2,2′-dihydroxy-4-methoxybenzophenone;    -   esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic        acid di-2-ethylhexyl ester;    -   triazine derivatives such as, for example,        2,4,6-trianilino-(p-carbo-2′-ethyl-1′-hexyloxy)-1,3,5-triazine        and Octyl Triazone as described in EP 0818450 A1 or Dioctyl        Butamido Triazone (Uvasorb® HEB);    -   propane-1,3-diones such as, for example,        1-(4-tert.butylphenyl)-3-(4′-methoxyphenyl)-propane-1,3-dione;    -   ketotricyclo(5.2.1.0)decane derivatives as described in EP        0694521 B1.

Suitable water-soluble substances are

-   -   2-phenylbenzimidazole-5-sulfonic acid and alkali metal, alkaline        earth metal, ammonium, alkylammonium, alkanolammonium and        glucammonium salts thereof;    -   sulfonic acid derivatives of benzophenones, preferably        2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and salts        thereof;    -   sulfonic acid derivatives of 3-benzylidene camphor such as, for        example, 4-(2-oxo-3-bornylidenemethyl)-benzene sulfonic acid and        2-methyl-5-(2-oxo-3-bornylidene)-sulfonic acid and salts        thereof.

Typical UV-A filters are, in particular, derivatives of benzoyl methanesuch as, for example,1-(4′-tert.butylphenyl)-3-(4′-methoxyphenyl)-propane-1,3-dione,4-tert.butyl4′-methoxydibenzoyl methane (Parsol 1789) or1-phenyl-3-(4′-isopropylphenyl)-propane-1,3-dione and the enaminecompounds described in DE 19712033 A1 (BASF). The UV-A and UV-B filtersmay of course also be used in the form of mixtures. Particularlyfavorable combinations consist of the derivatives of benzoyl methane,for example 4-tert.butyl-4′-methoxydibenzoylmethane (Parsol® 1789) and2-cyano-3,3-phenylcinnamic acid-2-ethyl hexyl ester (Octocrylene) incombination with esters of cinnamic acid, preferably 4-methoxycinnamicacid-2-ethyl hexyl ester and/or 4-methoxycinnamic acid propyl esterand/or 4-methoxycinnamic acid isoamyl ester. Combinations such as theseare advantageously combined with water-soluble filters such as, forexample, 2-phenylbenzimidazole-5-sulfonic acid and alkali metal,alkaline earth metal, ammonium, alkylammonium, alkanolammonium andglucammonium salts thereof.

Besides the soluble substances mentioned, insoluble light-blockingpigments, i.e. finely dispersed metal oxides or salts, may also be usedfor this purpose. Examples of suitable metal oxides are, in particular,zinc oxide and titanium dioxide and also oxides of iron, zirconiumoxide, silicon, manganese, aluminium and cerium and mixtures thereof.Silicates (talcum), barium sulfate and zinc stearate may be used assalts. The oxides and salts are used in the form of the pigments forskin-care and skin-protecting emulsions and decorative cosmetics. Theparticles should have a mean diameter of less than 100 nm, preferablybetween 5 and 50 nm and more preferably between 15 and 30 nm. They maybe spherical in shape although ellipsoidal particles or othernon-spherical particles may also be used. The pigments may also besurface-treated, i.e. hydrophilicized or hydrophobicized. Typicalexamples are coated titanium dioxides, for example Titandioxid T 805(Degussa) and Eusolex® T2000 (Merck). Suitable hydrophobic coatingmaterials are, above all, silicones and, among these, especiallytrialkoxyoctylsilanes or simethicones. So-called micro- or nanopigmentsare preferably used in sun protection products. Micronized zinc oxide ispreferably used. Other suitable UV filters can be found in P. Finkel'sreview in SÖFW-Journal 122, 543 (1996) and in Parf. Kosm. 3, 11 (1999).

Besides the two groups of primary sun protection factors mentionedabove, secondary sun protection factors of the antioxidant type may alsobe used. Secondary sun protection factors of the antioxidant typeinterrupt the photochemical reaction chain which is initiated when UVrays penetrate into the skin. Typical examples are amino acids (forexample glycine, histidine, tyrosine, tryptophane) and derivativesthereof, imidazoles (for example urocanic acid) and derivatives thereof,peptides, such as D,L-carnosine, D-carnosine, L-carnosine andderivatives thereof (for example anserine), carotinoids, carotenes (forexample α-carotene, β-carotene, lycopene) and derivatives thereof,chlorogenic acid and derivatives thereof, liponic acid and derivativesthereof (for example dihydroliponic acid), aurothioglucose,propylthiouracil and other thiols (for example thioredoxine,glutathione, cysteine, cystine, cystamine and glycosyl, N-acetyl,methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl,γ-linoleyl, cholesteryl and glyceryl esters thereof) and their salts,dilaurylthiodipropionate, distearylthiodipropionate, thiodipropionicacid and derivatives thereof (esters, ethers, peptides, lipids,nucleotides, nucleosides and salts) and sulfoximine compounds (forexample butionine sulfoximines, homocysteine sulfoximine, butioninesulfones, penta-, hexa- and hepta-thionine sulfoximine) in very smallcompatible dosages (for example pmol to μmol/kg), also (metal) chelators(for example α-hydroxyfatty acids, palmitic acid, phytic acid,lactoferrine), α-hydroxy acids (for example citric acid, lactic acid,malic acid), humic acid, bile acid, bile extracts, bilirubin,biliverdin, EDTA, EGTA and derivatives thereof, unsaturated fatty acidsand derivatives thereof (for example γ-linolenic acid, linoleic acid,oleic acid), folic acid and derivatives thereof, ubiquinone andubiquinol and derivatives thereof, vitamin C and derivatives thereof(for example ascorbyl palmitate, Mg ascorbyl phosphate, ascorbylacetate), tocopherols and derivatives (for example vitamin E acetate),vitamin A and derivatives (vitamin A palmitate) and coniferyl benzoateof benzoin resin, rutinic acid and derivatives thereof, α-glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butylhydroxytoluene, butyl hydroxyanisole, nordihydroguaiac resin acid,nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid andderivatives thereof, mannose and derivatives thereof,Superoxid-Dismutase, zinc and derivatives thereof (for example ZnO,ZnSO₄), selenium and derivatives thereof (for example seleniummethionine), stilbenes and derivatives thereof (for example stilbeneoxide, trans-stilbene oxide) and derivatives of these active substancessuitable for the purposes of the invention (salts, esters, ethers,sugars, nucleotides, nucleosides, peptides and lipids).

Biogenic Agents

In the context of the invention, biogenic agents are, for example,tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid,(deoxy)ribonucleic acid and fragmentation products thereof, β-glucans,retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, aminoacids, ceramides, pseudoceramides, essential oils, plant extracts, forexample prune extract, bambara nut extract, and vitamin complexes.

Deodorants and Germ Inhibitors

Cosmetic deodorants counteract, mask or eliminate body odors. Body odorsare formed through the action of skin bacteria on apocrine perspirationwhich results in the formation of unpleasant-smelling degradationproducts. Accordingly, deodorants contain active principles which act asgerm inhibitors, enzyme inhibitors, odor absorbers or odor maskers.

Germ Inhibitors

Basically, suitable germ inhibitors are any substances which act againstgram-positive bacteria such as, for example, 4-hydroxybenzoic acid andsalts and esters thereof,N-(4-chlorophenyl)-N′-(3,4-dichlorophenyl)-urea,2,4,4′-trichloro-2′-hydroxydiphenylether(triclosan),4-chloro-3,5-dimethylphenol,2,2′-methylene-bis-(6-bromo-4-chlorophenol),3-methyl-4-(1-methylethyl)-phenol, 2-benzyl-4-chlorophenol,3-(4-chlorophenoxy)-propane-1,2-diol, 3-iodo-2-propinyl butyl carbamate,chlorhexidine, 3,4,4′-trichlorocarbanilide (TTC), antibacterialperfumes, thymol, thyme oil, eugenol, clove oil, menthol, mint oil,farnesol, phenoxyethanol, glycerol monocaprate, glycerol monocaprylate,glycerol monolaurate (GML), diglycerol monocaprate (DMC), salicylicacid-N-alkylamides such as, for example, salicylic acid-n-octyl amide orsalicylic acid-n-decyl amide.

Enzyme Inhibitors

Suitable enzyme inhibitors are, for example, esterase inhibitors.Esterase inhibitors are preferably trialkyl citrates, such as trimethylcitrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and,in particular, triethyl citrate (Hydagen® CAT). Esterase inhibitorsinhibit enzyme activity and thus reduce odor formation. Other esteraseinhibitors are sterol sulfates or phosphates such as, for example,lanosterol, cholesterol, campesterol, stigmasterol and sitosterolsulfate or phosphate, dicarboxylic acids and esters thereof, for exampleglutaric acid, glutaric acid monoethyl ester, glutaric acid diethylester, adipic acid, adipic acid monoethyl ester, adipic acid diethylester, malonic acid and malonic acid diethyl ester, hydroxycarboxylicacids and esters thereof, for example citric acid, malic acid, tartaricacid or tartaric acid diethyl ester, and zinc glycinate.

Odor Absorbers

Suitable odor absorbers are substances which are capable of absorbingand largely retaining the odor-forming compounds. They reduce thepartial pressure of the individual components and thus also reduce therate at which they spread. An important requirement in this regard isthat perfumes must remain unimpaired. Odor absorbers are not activeagainst bacteria. They contain, for example, a complex zinc salt ofricinoleic acid or special perfumes of largely neutral odor known to theexpert as “fixateurs” such as, for example, extracts of ladanum orstyrax or certain abietic acid derivatives as their principal component.Odor maskers are perfumes or perfume oils which, besides theirodor-masking function, impart their particular perfume note to thedeodorants. Suitable perfume oils are, for example, mixtures of naturaland synthetic fragrances. Natural fragrances include the extracts ofblooms, stems and leaves, fruits, fruit peel, roots, woods, herbs andgrasses, needles and branches, resins and balsams. Animal raw materials,for example civet and beaver, may also be used. Typical syntheticperfume compounds are products of the ester, ether, aldehyde, ketone,alcohol and hydrocarbon type. Examples of perfume compounds of the estertype are benzyl acetate, p-tert.butyl cyclohexylacetate, linalylacetate, phenyl ethyl acetate, linalyl benzoate, benzyl formate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate.Ethers include, for example, benzyl ethyl ether while aldehydes include,for example, the linear alkanals containing 8 to 18 carbon atoms,citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde,hydroxycitronellal, lilial and bourgeonal. Examples of suitable ketonesare the ionones and methyl cedryl ketone. Suitable alcohols are anethol,citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethylalcohol and terpineol. The hydrocarbons mainly include the terpenes andbalsams. However, it is preferred to use mixtures of different perfumecompounds which, together, produce an agreeable fragrance. Othersuitable perfume oils are essential oils of relatively low volatilitywhich are mostly used as aroma components. Examples are sage oil,camomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil,lime-blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanumoil, ladanum oil and lavendin oil. The following are preferably usedeither individually or in the form of mixtures: bergamot oil,dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol,α-hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde,linalool, Boisambrene Forte, Ambroxan, indole, hedione, sandelice,citrus oil, mandarin oil, orange oil, allylamyl glycolate, cyclovertal,lavendin oil, clary oil, β-damascone, geranium oil bourbon, cyclohexylsalicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iraldeingamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide,romillat, irotyl and floramat.

Antiperspirants

Antiperspirants reduce perspiration and thus counteract underarm wetnessand body odor by influencing the activity of the eccrine sweat glands.Aqueous or water-free antiperspirant formulations typically contain thefollowing ingredients:

-   -   astringent active principles,    -   oil components,    -   nonionic emulsifiers,    -   co-emulsifiers,    -   consistency factors,    -   auxiliaries in the form of, for example, thickeners or        complexing agents and/or    -   non-aqueous solvents such as, for example, ethanol, propylene        glycol and/or glycerol.

Suitable astringent active principles of antiperspirants are, above all,salts of aluminium, zirconium or zinc. Suitable antihydrotic agents ofthis type are, for example, aluminium chloride, aluminium chlorohydrate,aluminium dichlorohydrate, aluminium sesquichlorohydrate and complexcompounds thereof, for example with 1,2-propylene glycol, aluminiumhydroxyallantoinate, aluminium chloride tartrate, aluminium zirconiumtrichlorohydrate, aluminium zirconium tetrachlorohydrate, aluminiumzirconium pentachlorohydrate and complex compounds thereof, for examplewith amino acids, such as glycine. Oil-soluble and water-solubleauxiliaries typically encountered in antiperspirants may also be presentin relatively small amounts. Oil-soluble auxiliaries such as theseinclude, for example,

-   -   inflammation-inhibiting, skin-protecting or pleasant-smelling        essential oils,    -   synthetic skin-protecting agents and/or    -   oil-soluble perfume oils.

Typical water-soluble additives are, for example, preservatives,water-soluble perfumes, pH adjusters, for example buffer mixtures,water-soluble thickeners, for example water-soluble natural or syntheticpolymers such as, for example, xanthan gum, hydroxyethyl cellulose,polyvinyl pyrrolidone or high molecular weight polyethylene oxides.

Film Formers

Standard film formers are, for example, chitosan, microcrystallinechitosan, quaternized chitosan, polyvinyl pyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, polymers of the acrylic acidseries, quaternary cellulose derivatives, collagen, hyaluronic acid andsalts thereof and similar compounds.

Antidandruff Agents

Suitable antidandruff agents are Pirocton Olamin(1-hydroxy4-methyl-6-(2,4,4-trimethylpentyl)-2-(1H )-pyridinonemonoethanolamine salt), Baypival® (Climbazole), Ketoconazol®(4-acetyl-1-{4-[2-(2,4-dichlorophenyl)r-2-(1H-imidazol-1-ylmethyl)-1,3-dioxylan-c-4-ylmethoxy-phenyl}-piperazine,ketoconazole, elubiol, selenium disulfide, colloidal sulfur, sulfurpolyethylene glycol sorbitan monooleate, sulfur ricinol polyethoxylate,sulfur tar distillate, salicylic acid (or in combination withhexachlorophene), undecylenic acid, monoethanolamide sulfosuccinate Nasalt, Lamepon® UD (protein/undecylenic acid condensate), zincpyrithione, aluminium pyrithione and magnesium pyrithione/dipyrithionemagnesium sulfate.

Swelling Agents

Suitable swelling agents for aqueous phases are montmorillonites, clayminerals, Pemulen and alkyl-modified Carbopol types (Goodrich). Othersuitable polymers and swelling agents can be found in R. Lochhead'sreview in Cosm. Toil. 108, 95 (1993).

Insect Repellents

Suitable insect repellents are N,N-diethyl-m-toluamide, pentane-1,2-diolor Ethyl Butylacetylaminopropionate.

Self-Tanning Agents and Depigmentinq Agents

A suitable self-tanning agent is dihydroxyacetone. Suitable tyrosineinhibitors which prevent the formation of melanin and are used indepigmenting agents are, for example, arbutin, ferulic acid, koji acid,coumaric acid and ascorbic acid (vitamin C).

Hydrotropes

In addition, hydrotropes, for example ethanol, isopropyl alcohol orpolyols, may be used to improve flow behavior. Suitable polyolspreferably contain 2 to 15 carbon atoms and at least two hydroxylgroups. The polyols may contain other functional groups, more especiallyamino groups, or may be modified with nitrogen. Typical examples are

-   -   glycerol;    -   alkylene glycols such as, for example, ethylene glycol,        diethylene glycol, propylene glycol, butylene glycol, hexylene        glycol and polyethylene glycols with an average molecular weight        of 100 to 1000 dalton;    -   technical oligoglycerol mixtures with a degree of        self-condensation of 1.5 to 10 such as, for example, technical        diglycerol mixtures with a diglycerol content of 40 to 50% by        weight;    -   methylol compounds such as, in particular, trimethylol ethane,        trimethylol propane, trimethylol butane, pentaerythritol and        dipentaerythritol;    -   lower alkyl glucosides, particularly those containing 1 to 8        carbon atoms in the alkyl group, for example methyl and butyl        glucoside;    -   sugar alcohols containing 5 to 12 carbon atoms, for example        sorbitol or mannitol,    -   sugars containing 5 to 12 carbon atoms, for example glucose or        sucrose;    -   amino sugars, for example glucamine;    -   dialcoholamines, such as diethanolamine or        2-aminopropane-1,3-diol.        Preservatives

Suitable preservatives are, for example, phenoxyethanol, formaldehydesolution, parabens, pentanediol or sorbic acid and the silver complexesknown under the name of Surfacine® and the other classes of compoundslisted in Appendix 6, Parts A and B of the Kosmetikverordnung(“Cosmetics Directive”).

Perfume Oils and Aromas

Suitable perfume oils are mixtures of natural and synthetic perfumes.Natural perfumes include the extracts of blossoms (lily, lavender, rose,jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli,petitgrain), fruits (anise, coriander, caraway, juniper), fruit peel(bergamot, lemon, orange), roots (nutmeg, angelica, celery, cardamom,costus, iris, calmus), woods (pinewood, sandalwood, guaiac wood,cedarwood, rosewood), herbs and grasses (tarragon, lemon grass, sage,thyme), needles and branches (spruce, fir, pine, dwarf pine), resins andbalsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animalraw materials, for example civet and beaver, may also be used. Typicalsynthetic perfume compounds are products of the ester, ether, aldehyde,ketone, alcohol and hydrocarbon type. Examples of perfume compounds ofthe ester type are benzyl acetate, phenoxyethyl isobutyrate,p-tert.butyl cyclohexylacetate, linalyl acetate, dimethyl benzylcarbinyl acetate, phenyl ethyl acetate, linalyl benzoate, benzylformate, ethylmethyl phenyl glycinate, allyl cyclohexyl propionate,styrallyl propionate and benzyl salicylate. Ethers include, for example,benzyl ethyl ether while aldehydes include, for example, the linearalkanals containing 8 to 18 carbon atoms, citral, citronellal,citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxy-citronellal,lilial and bourgeonal. Examples of suitable ketones are the ionones,α-isomethylionone and methyl cedryl ketone. Suitable alcohols areanethol, citronellol, eugenol, isoeugenol, geraniol, linalool,phenylethyl alcohol and terpineol. The hydrocarbons mainly include theterpenes and balsams. However, it is preferred to use mixtures ofdifferent perfume compounds which, together, produce an agreeableperfume. Other suitable perfume oils are essential oils of relativelylow volatility which are mostly used as aroma components. Examples aresage oil, camomile oil, clove oil, melissa oil, mint oil, cinnamon leafoil, lime-blossom oil, juniper berry oil, vetiver oil, olibanum oil,galbanum oil, ladanum oil and lavendin oil. The following are preferablyused either individually or in the form of mixtures: bergamot oil,dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol,α-hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde,linalool, Boisambrene Forte, Ambroxan, indole, hedione, sandelice,citrus oil, mandarin oil, orange oil, allylamyl glycolate, cyclovertal,lavendin oil, clary oil, β-damascone, geranium oil bourbon, cyclohexylsalicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iraldeingamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide,romillat, irotyl and floramat.

Suitable aromas are, for example, peppermint oil, spearmint oil, aniseedoil, Japanese anise oil, caraway oil, eucalyptus oil, fennel oil, citrusoil, wintergreen oil, clove oil, menthol and the like.

Dyes

Suitable dyes are any of the substances suitable and approved forcosmetic purposes as listed, for example, in the publication“Kosmetische Färbemittel” of the Farbstoffkommission der DeutschenForschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, pages 81 to 106.Examples include cochineal red A (C.I. 16255), patent blue V (C.I.42051), indigotin (C.I. 73015), chlorophyllin (C.I. 75810), quinolineyellow (C.I. 47005), titanium dioxide (C.I. 77891), indanthrene blue RS(C.I. 69800) and madder lake (C.I. 58000). Luminol may also be presentas a luminescent dye. These dyes are normally used in concentrations of0.001 to 0.1% by weight, based on the mixture as a whole.

The total percentage content of auxiliaries and additives may be from 1to 50% by weight and is preferably from 5 to 40% by weight, based on theparticular preparations. The preparations may be produced by standardhot or cold processes and are preferably produced by the phase inversiontemperature method.

EXAMPLES Production Example 1

406 g (2.82 mol) caprylic acid, 206 g (1.41 mol) adipic acid and 0.8 gsodium hypophosphite were introduced into a 2-liter three-necked flaskequipped with a stirrer, distillation head and vacuum connection andheated to 70° C. The pressure was then reduced to 35 mbar and 420 g(2.82 mol) triethanolamine were added in portions. The temperature wasincreased in steps to 165° C. and the pressure was reduced to 5 mbaruntil the separation of water stopped and the acid value had fallen to avalue below 5 mg KOH/g. 871 g (2.72 mol) of the ester thus produced weretransferred to a second flask and dissolved at 50° C. in 211 g isopropylalcohol. 324 g (2.57 mol) dimethyl sulfate were then added in portionswith stirring, the temperature being kept at 70° C. for 4 hours.

Production Example 2

424 g (2.73 mol) of a technical 1:1 mixture of caprylic and capric acid,200 g (1.37 mol) adipic acid, 0.7 g sodium hypophosphite and 408 g (2.74mol) triethanolamine were reacted as in Example 1. 871 g (2.63 mol) ofthe resulting ester were then dissolved in 132 g isopropyl alcohol andquaternized with 315 g (2.5 mol) dimethyl sulfate.

Production Example 3

292 g (1.70 mol) capric acid, 124 g (0.85 mol) adipic acid, 0.5 g sodiumhypophosphite and 253 g (1.70 mol) triethanolamine were reacted as inExample 1. 582 g (1.63 mol) of the resulting ester were then dissolvedin 137 g isopropyl alcohol and quaternized with 194 g (1.54 mol)dimethyl sulfate.

A number of Formulation Examples are shown in Table 1.

TABLE 1 Examples of cosmetic preparations (water, preservative to 100%by weight) Composition(INCI) 1 2 3 4 5 6 7 8 9 10 Texapon ® NSO — — — —— — 38.0  38.0  25.0  — Sodium Laureth Sulfate Texapon ® SB 3 — — — — —— — — 10.0  — Disodium Laureth Sulfosuccinate Plantacare ® 818 — — — — —— 7.0 7.0 6.0 — Coco Glucosides Plantacare ® PS 10 — — — — — — — — —16.0  Sodium Laureth Sulfate (and) Coco Glucosides Dehyton ® PK 45 — — —— — — — — 10.0  — Cocamidopropyl Betaine Dehyquart ® A 2.0 2.0 2.0 2.04.0 4.0 — — — — Cetrimonium Chloride Dehyquart L ® 80 1.2 1.2 1.2 1.20.6 0.6 — — — — Dococoylmethylethoxymonium Methosulfate (and)Propyleneglycol Dehyquart ® ABIO-8 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.01.0 Capryloyl/Adipinoyl Methylethoxymonium Methodsulfate Eumulgin ® B20.8 0.8 — 0.8 — 1.0 — — — — Ceteareth-20 Eumulgin ® VL 75 — — 0.8 — 0.8— — — — — Lauryl Glucoside (and) Polyglyceryl-2 Polyhydroxystearate(and) Glycerin Lanette ® O 2.5 2.5 2.5 2.5 3.0 2.5 — — — — CetearylAlcohol Cutina ® GMS 0.5 0.5 0.5 0.5 0.5 1.0 — — — — Glyceryl StearateCetiol ® HE 1.0 — — — — — — — 1.0 — PEG-7 Glyceryl Cocoate Cetiol ® PGL— 1.0 — — 1.0 — — — — — Hexyldecanol (and) Hexyldecyl laurate Cetiol ® V— — — 1.0 — — — — — — Decyl Oleate Eutanol ® G — — 1.0 — — 1.0 — — — —Octyldodecanol Nutrilan ® Keratin W — — — 2.0 — — — — — — HydrolyzedKeratin Lamesoft ® LMG — — — — — — 3.0 2.0 4.0 — Glyceryl Laurate (and)Potassium Cocoyl Hydrolyzed Collagen Euperlan ® PK 3000 AM — — — — — — —3.0 5.0 5.0 Glycol Distearate (and) Laureth-4 (and) CocamidopropylBetaine Generol ® 122 N — — — — 1.0 1.0 — — — — Soya Sterol Hydagen ®CMF 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Chitosan Copherol ® 1250 — —0.1 0.1 — — — — — — Tocopherol Acetate Arlypon ® F — — — — — — 3.0 3.01.0 — Laureth-2 Sodium Chloride — — — — — — — 1.5 — 1.5 Composition(INCI) 11 12 13 14 15 16 17 18 19 20 Texapon ® NSO 20.0  20.0  12.4  —25.0  11.0  — — — — Sodium Laureth Sulfate Texpon ® K 14 S — — — — — — —— 11.0  23.0  Sodium Myreth Sulfate Texapon ® SB 3 — — — — — 7.0 — — — —Disodium Laureth Sulfosuccinate Plantacare ® 818 5.0 5.0 4.0 — — — — —6.0 4.0 Coco Glucosides Plantacare ® 2000 — — — — 5.0 4.0 — — — — DecylGlucoside Plantacare ® PS 10 — — — 40.0  — — 16.0  17.0  — — SodiumLaureth Sulfate (and) Coco Glucosides Dehyton ® PK 45 20.0  20.0  — —8.0 — — — — 7.0 Cocamidopropyl Betaine Dehyquart ® ABIO-8 1.0 1.0 1.01.0 1.0 1.0 1.0 1.0 1.0 1.0 Capryloyl/Adipinoyl MethylethoxymoniumMethodsulfate Eumulgin ® B1 — — — — 1.0 — — — — — Ceteareth-12Eumulgin ® B2 — — — 1.0 — — — — — — Ceteareth-20 Lameform ® TGI — — —4.0 — — — — — — Polyglyceryl-3 Isostearate Dehymuls ® PGPH — — 1.0 — — —— — — — Polyglyceryl-2 Dipolyhydroxystearate Monomuls ® 90-L 12 — — — —— — — — 1.0 1.0 Glyceryl Laurate Cetiol ® HE — 0.2 — — — — — — — — PEG-7Glyceryl Cocoate Eutanol ® G — — — 3.0 — — — — — — OctyldodecanolNutrilan ® Keratin W — — — — — — — — 2.0 2.0 Hydrolyzed KeratinNutrilan ® I 1.0 — — — — 2.0 — 2.0 — — Hydrolyzed Collagen Lamesoft ®LMG — — — — — — — — 1.0 — Glyceryl Laurate (and) Potassium CocoylHydrolyzed Collagen Lamesoft ® 156 — — — — — — — — — 5.0 HydrogenatedTallow Glyceride (and) Potassium Cocoyl Hyrolyzed Collagen Gluadin ® WK1.0 1.5 4.0 1.0 3.0 1.0 2.0 2.0 2.0 — Sodium Cocoyl Hydrolyzed WheatProtein Euperlan ® PK 3000 AM 5.0 3.0 4.0 — — — — 3.0 3.0 — GlycolDistearate (and) Laureth-4 (and) Cocamidopropyl Betaine Arlypon ® F 2.61.6 — 1.0 1.5 — — — — — Laureth-2 Hydagen ® CMF 1.0 1.0 1.0 1.0 1.0 1.01.0 1.0 1.0 1.0 Chitosan Sodium Chloride — — — — — 1.6 2.0 2.2 — 3.0Glycerin (86% by weight) — 5.0 — — — — — 1.0 3.0 — Composition (INCI) 2122 23 24 25 26 27 28 29 30 Texapon ® NSO — 30.0  30.0  — 25.0  — — — — —Sodium Laureth Sulfate Plantacare ® 818 — 10.0  — — 20.0  — — — — — CocoGlucosides Plantacare ® PS 10 22.0  — 5.0 22.0  — — — — — — SodiumLaureth Sulfate (and) Coco Glucosides Dehyton ® PK 45 15.0  10.0  15.0 15.0  20.0  — — — — — Cocamidopropyl Betaine Dehyquart ® ABIO-8 1.0 1.01.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Capryloyl/Adipinoyl MethylethoxymoniumMethodsulfate Emulgade ® SE — — — — — 5.0 5.0 4.0 — — Glyceryl Stearate(and) Ceteareth 12/20 (and) Cetearyl Alcohol (and) Cetyl PalmitateEumulgin ® B1 — — — — — — — 1.0 — — Ceteareth-12 Lameform ® TGI — — — —— — — — 4.0 — Polyglyceryl-3 Isostearate Dehymuls ® PGPH — — — — — — — —— 4.0 Polyglyceryl-2 Dipolyhydroxystearate Monomuls ® 90-O 18 — — — — —— — — 2.0 — Glyceryl Oleate Cetiol ® HE 2.0 — — 2.0 5.0 — — — — 2.0PEG-7 Glyceryl Cocoate Cetiol ® OE — — — — — — — — 5.0 6.0 DicaprylylEther Cetiol ® PGL — — — — — — — 3.0 10.0  9.0 Hexyldecanol (and)Hexyldecyl Laurate Cetiol ® SN — — — — — 3.0 3.0 — — — CetearylIsononanoate Cetiol ® V — — — — — 3.0 3.0 — — — Decyl Oleate Myritol ®318 — — — — — — — 3.0 5.0 5.0 Coco Caprylate Caprate Bees Wax — — — — —— — — 7.0 5.0 Nutrilan ® Elastin E20 — — — — — 2.0 — — — — HydrolyzedElastin Nutrilan ® I-50 — — — — 2.0 — 2.0 — — — Hydrolyzed CollagenGluadin ® AGP 0.5 0.5 0.5 — — — — 0.5 — — Hydrolyzed Wheat GlutenGluadin ® WK 2.0 2.0 2.0 2.0 5.0 — — — 0.5 0.5 Sodium Cocoyl HydrolyzedWheat Protein Euperlan ® PK 3000 AM 5.0 — — 5.0 — — — — — — GlycolDistearate (and) Laureth-4 (and) Cocamidopropyl Betaine Arlypon ® F — —— — — — — — — — Laureth-2 Hydagen ® CMF 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.01.0 1.0 Chitosan Magnsium Sulfate Hepta Hydrate — — — — — — — — 1.0 1.0Glycerin (85% by weight) — — — — — 3.0 3.0 5.0 5.0 3.0 Composition(INCI) 31 32 33 34 35 36 37 38 39 40 Dehymuls ® PGPH 4.0 3.0 — 5.0 — — —— — — Polyglyceryl-2 Dipolyhydroxystearate Lameform ® TGI 2.0 1.0 — — —— — — — — Polyglyceryl-3 Diisostearate Emulgade ® PL 68/50 — — — — 4.0 —— — 3.0 — Cetearyl Glucoside (and) Cetearyl Alcohol Eumulgin ® B2 — — —— — — — 2.0 — — Ceteareth-20 Tegocare ® PS — — 3.0 — — — 4.0 — — —Polyglyceryl-3 Methylglucose Distearate Eumulgin VL 75 — — — — — 3.5 — —2.5 — Polyglyceryl-2 Dipolyhydroxystearate (and) Lauryl Glucoside (and)Glycerin Dehyquart ® ABIO-8 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0Capryloyl/Adipinoyl Methylethoxymonium Methodsulfate Bees Wax 3.0 2.05.0 2.0 — — — — — — Cutina ® GMS — — — — — 2.0 4.0 — — 4.0 GlycerylStearate Lanette ® O — — 2.0 — 2.0 4.0 2.0 4.0 4.0 1.0 Cetearyl AlcoholAntaron ® V 216 — — — — — 3.0 — — — 2.0 PVP/Hexadecene CopolymerMyritol ® 818 5.0 — 10.0 — 8.0 6.0 6.0 — 5.0 5.0 CocoglyceridesFinsolv ® TN — 6.0 — 2.0 — — 3.0 — — 2.0 C12/15 Alkyl Benzoate Cetiol ®J 600 7.0 4.0 3.0 5.0 4.0 3.0 3.0 — 5.0 4.0 Oleyl Erucate Cetiol ® OE3.0 — 6.0 8.0 6.0 5.0 4.0 3.0 4.0 6.0 Dicaprylyl Ether Mineral Oil — 4.0— 4.0 — 2.0 — 1.0 — — Cetiol ® PGL — 7.0 3.0 7.0 4.0 — — — 1.0 —Hexadecanol (and) Hexyldecyl Laurate Bisabolol 1.2 1.2 1.2 1.2 1.2 1.21.2 1.2 1.2 1.2 Hydagen ® CMF 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0Chitosan Copherol ® F 1300 0.5 1.0 1.0 2.0 1.0 1.0 1.0 2.0 0.5 2.0Tocopherol/Tocopheryl Acetate Neo Heliopan ® Hydro 3.0 — — 3.0 — — 2.0 —2.0 — Sodium Phenylbenzimidazole Sulfonate Neo Heliopan ® 303 — 5.0 — —— 4.0 5.0 — — 10.0  Octocrylene Neo Heliopan ® BB 1.5 — — 2.0 1.5 — — —2.0 — Benzophenone-3 Neo Heliopan ® E 1000 5.0 — 4.0 — 2.0 2.0 4.0 10.0 — — Isoamyl p-Methoxycinnamate Neo Heliopan ® AV 4.0 — 4.0 3.0 2.0 3.04.0 — 10.0 2.0 Octyl Methoxycinnamate Uvinul ® T 150 2.0 4.0 3.0 1.0 1.01.0 4.0 3.0 3.0 3.0 Octyl Triazone Zinc Oxide — 6.0 6.0 — 4.0 — — — —5.0 Titanium Dioxide — — — — — — — 5.0 — — Glycerol (86% by weight) 5.05.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 (1-4) Hair rinse, (5-6) Conditioner,(7-8) Shower bath, (9) Shower gel, (10) Wash lotion (11-14) “Two-in-one”shower bath, (15-20) Shampoo (21-25) Foam bath, (26) Soft cream, (27,28) Moisturising emulsion, (29, 30) Night cream (31) W/O sun protectioncream, (32-34) W/O sun protection lotion, (35, 38, 40) O/W sunprotection lotion, (36, 27, 39) 0/W sun protection cream

1. A method of improving the stability of a composition containing along-chain esterquat, said method comprising: (a) providing acomposition containing a long-chain esterquat; (b) providing ashort-chain esterquat having acyl groups derived from a mixture of atleast one monocarboxylic acid having from 6 to 10 carbon atoms, and atleast one dicarboxylic acid having from 2 to 12 carbon atoms; and (c)combining the composition and the short-chain esterquat.
 2. The methodaccording to claim 1, wherein the at least one monocarboxylic acidcomprises an acid corresponding to the general formula (I):R¹CO—OH  (I) wherein R¹CO represents an acyl group having from 6 to 10carbon atoms.
 3. The method according to claim 2, wherein R¹COrepresents a linear, saturated acyl group having from 8 to 10 carbonsatoms.
 4. The method according to claim 1, wherein the at least onedicarboxylic acid comprises an acid corresponding to the general formula(II):HOOC(CH₂)_(n)COOH  (II) wherein n represents a number of from 1 to 10.5. The method according to claim 1, wherein the at least onedicarboxylic acid comprises adipic acid.
 6. The method according toclaim 3, wherein the at least one dicarboxylic acid comprises adipicacid.
 7. The method according to claim 1, wherein the acyl groupsderived from the at least one monocarboxylic acid and the acyl groupsderived from the at least one dicarboxylic acid are present in a molarratio of from 50:50 to 90:10.
 8. The method according to claim 1,wherein the acyl groups derived from the at least one monocarboxylicacid and the acyl groups derived from the at least one dicarboxylic acidare present in a molar ratio of from 70:30 to 80:20.
 9. The methodaccording to claim 1, wherein the short-chain esterquat is combined withthe composition in an amount of from 0.1 to 10% by weight, based on thecomposition.
 10. The method according to claim 1, wherein theshort-chain esterquat is combined with the composition in an amount offrom 1 to 8% by weight, based on the composition.
 11. A method ofimproving the microbicidal properties of a cosmetic composition, saidmethod comprising: (a) providing a cosmetic composition containing atleast one component subject to microbial spoiling; (b) providing ashort-chain esterquat having acyl groups derived from a mixture of atleast one monocarboxylic acid having from 6 to 10 carbon atoms, and atleast one dicarboxylic acid having from 2 to 12 carbon atoms; and (c)combining the cosmetic composition and the short-chain esterquat. 12.The method according to claim 11, wherein the at least onemonocarboxylic acid comprises an acid corresponding to the generalformula (I):R¹CO—OH  (I) wherein R¹CO represents an acyl group having from 6 to 10carbon atoms.
 13. The method according to claim 12, wherein R¹COrepresents a linear, saturated acyl group having from 8 to 10 carbonsatoms.
 14. The method according to claim 11, wherein the at least onedicarboxylic acid comprises an acid corresponding to the general formula(II):HOOC(CH₂)_(n)COOH  (II) wherein n represents a number of from 1 to 10.15. The method according to claim 11, wherein the at least onedicarboxylic acid comprises adipic acid.
 16. The method according toclaim 13, wherein the at least one dicarboxylic acid comprises adipicacid.
 17. The method according to claim 11, wherein the acyl groupsderived from the at least one monocarboxylic acid and the acyl groupsderived from the at least one dicarboxylic acid are present in a molarratio of from 50:50 to 90:10.
 18. The method according to claim 11,wherein the acyl groups derived from the at least one monocarboxylicacid and the acyl groups derived from the at least one dicarboxylic acidare present in a molar ratio of from 70:30 to 80:20.
 19. The methodaccording to claim 11, wherein the short-chain esterquat is combinedwith the composition in an amount of from 0.1 to 10% by weight, based onthe composition.
 20. The method according to claim 11, wherein theshort-chain esterquat is combined with the composition in an amount offrom 1 to 8% by weight, based on the composition.